Yeing and printing of textile fibers by means of dyes formed by oxidation



Patented Aug. 8, 1933 UNITED STATES PATENT OFFICE XEING AND PRINTING 0F TEXTILE FIBERS BY MEANS OF DYES FORMED BY OXIDA- TION Martin Battegay, Mulhouse, France, assignor to Calco Chemical Company, Inc., a Corporation of New Jersey No Drawing.

Application August 13, 1930 Serial No. 475,116

Claims.

My invention relates particularly to a process of dyeing and printing of fibres by means of dyes formed by oxidation and relates to the dyeing oi? fibers or fabrics of any desired character;

The object of my invention is to provide an improved process of the above character in which dyeing may be carried out in an advantageous manner by use of the materlals'as hereinafter referred to. In my previous application upon Process for the preparation of sultocyanateeomplex paraphenylenediamine and similar amines, Ser. No. 399,392, filed October 12, 1929, I'have described the preparation 01 a complex sulfucyanate of paraphenylenediamine and the'application of the same in dyeing. As an improvement over the same I have discovered'that the dyeing and printing of fibers, particularly textile fibers of any desired kind, as for example, cotton, may,

may mention among the products of transforma- 1 tion of the sulfocyanates, for the phenylenedithioureas and the monoaminophenylthio ureas; and then among the homologous derivatives or substitution products, the toluylene ditioureas and the monoaminotoluylthioureas; and finally, among the similarproducts, for instance, the compounds resulting from the condensation of aldehyde or ketone bisulfite addition products with amines, such as the sodium salt of methylaminophenyl-w-sulfonic acid, and the sodium salts of the methylaminotoluyl-w-sulionic acids, the sodium salts of the monomethylphenylenediamine-w-sulfonic acids, and the sodium salts of the phenyl-monomethylphenylenediamine-w-sulfonic acids, etc.

As pointed out above, these products are capable of being used in place of the products mentioned in the above application for Letters Patent in combination with the usual dyes formed by oxidation or alone to secure the same type of dyeing with the aid of oxidation. When used in the place of the product referred to in the above application for letters Patent, these products used in accordance with the present application can be directly incorporated in the dye solutions or printing pastes of the dyes of the usual type made by oxidation in order to apply them to the fibrous materials, or if desired, they can be applied separately to said materials by having them preceded or followed by the usual oxidized dy s.

While my invention is capable of being carried out in many difierent ways, for the purpose of illustration I shall now describe certain examples of the same:

1st example for the preparation of the due both gms. an aniline salt 150 cc. water 30 gms. sodium chlorate 150 cc. water 3 to 8 gms. of phenylenedithiourea, or the equivalent quantity of monoaminophenyl- 75 thiourea, or the sodium salt of monomethylphenylenediamine-w-su l f o n i 0 acid, or the sodium salt of phenylmonomethylphenylenediamine-w-su l f o n i 0 acid, and 100 cc. of 20% acetic acid 60 gms. sodium ferrocyanide dissolved in 150 cc. water The whole being diluted if desired to 1 liter solution.

2nd example for the preparation of the dye bath 75 gms. of aniline salt 150 cc. of water 30 gms. of sodium chlorate 150 cc. water 3 to 8 gms. of phenylenedithiourea, or the equivalent quantity of mono-aminophenylthiourea, or the sodium salt of monomethylphenylenediamine-sulfonic acid, or the sodium salt of phenylmonomethylphenylenediamine o: sulfonic acid cc. of 20% acetic acid, and

8 cc. of ammonium vanadate (1: 1000) The whole, if desired, in the above example 100 may be diluted to one liter by adding water.

For dyeing, in accordance with these examples, the textile fiber is impregnated with one of the preceding preparations, then centrifuged or pressed, and dried at a temperature not above 55 C. The color is developed either by a short usual steaming or by a prolonged airing, such as is customary for the development of oxidized colors. The dyed fiber is afterward passed through a dilute sodium carbonate bath comprising water containing 5% by weight of sodium carbonate to which has been added, if need be,

the usual quantity of an alkaline ohromate, that A Solution A is prepared containing 24 cc. aniline oil 24 cc. 22 B. hydrochloric acid 2 gms. of tartaric acid, and 150 cc. of water A Solution B is made containing 7 gms. of sodium chlorate 5.5 gms. of copper sulfate 5.5 gms. of ammonium chloride 200 cc. of water and finally Solution C containing 3 to 8 gms. of sodium monomethylphenylenediamine-w-sulfonate, or of sodium phenylmonomethylphenylendiamine-w-sulfonate, and 100 cc. of water The three solutions, A, B and C may be mixed just before being used and the operation is then carried out as under Examples 1 and 2.

The composition of this preparation can be equally well used for printing by proceeding as mentioned above, on the one hand by replacing a part of the water by a suitable thickener, and on the other hand by replacing the copper sulfate by 5 gms. of an insoluble copper salt, such as copper sulfide, for instance.

In the case where the above mentioned products precipitate with copper salts, the impregnation is carried out in two operations by mil!- ing the textile, for instance, in a first operation with a solution of 3 to 8 gms. of monoaminophenylthiourea dissolved in 40 cc. of 20% acetic acid and 960 cc. of water and then, after squeezing, passing in a mixture of Solutions A and B above mentioned.

To illustrate those of the above similar products which lend themselves to obtaining practical oxidized dyes, we will mention, for instance, the sodium salt of methylaminophenyl-sulfonic acid, or the sodium salt of methylaminoorthotoluylsulfonic acid, which yield intense brown colors by applying on the fiber, for instance, one of the following preparations:

4th example for the preparation of the dye bath 200 gms. of sodium methyl-aminophenyl-w-sulfonate, or of sodium methyl-aminoorthotoluyl-w-sulfonate cc. water to 100 gms. of sodium chlorate gms. of ammonium chloride cc. water cc. of vanadyl chloride (111000) example for the preparation of a dye bath gms. of sodium methyl-aminophenyl-w-sulfonate, or of sodium methylaminoorthotoluyl-w-sulfonate 300 cc. water to 100 gms. of sodium chlorate 20 gms. of ammonium chloride 20 cc. of a 50% copper sulfate solution, and 385cc. water.

The application on the fiber may be carried out exactly under the same conditions as given in Examples 1, 2 and 3.

It can also be carried out according to the printing method by making the above mentioned modifications, for example as referred to under the 2nd example.

In the above examples the sodium chlorate acts as an oxidizing agent; the acetic acid, hydrochloric acid, and tartaric acid are provided to control the color desired and as solvents; the ammonium vanadate and the vanadyl chlorate assist in the oxidation and act as catalysts; the copper sulfate acts as a catalyst and also assists in the oxidation.

While I have described my invention above in detail, it is to be understood that many changes may be made therein without departing from the spirit of the same as set forth in the claims.

I claim:

1. The process which comprises dyeing a fibrous material with the aid of a dyeing composition containing a member of a group of substances which consists of transformation products of sulfocyanate derivatives of the benzene series.

2. The process which comprises dyeing a fibrous material with the aid of a dyeing composition containing a phenylene dithiourea.

3. The process which comprises dying a fibrous material with the aid of a dyeing composition containing a dye formed by oxidation, and as another dye, a member of a group of substances which consists of transformation products of sulfocyanate derivatives of the benzene series.

4. The process which comprises dyeing a librous material with the aid of a dyeing composition containing a dye formed by oxidation, and as another dye, a phenylene dithiourea.

5. The process which comprises dyeing a fibrous material with the aid of a dyeing composition containing a dye formed by oxidation, and as another dye, a member of a group of substances which consists of transformation products of sulfocyanate derivatives of the benzene series, one of said dyes being applied first and the other dye being applied later to the fibrous material to be dyed.

6. The process which comprises dyeing a fibrous material with the aid of a dyeing composition containing a dye formed by oxidation, and as another dye, a. member of a group of substances which consists of transformation products of sulfocyanates of the benzene series, one of said dyes being applied first and the other dye being applied later to the fibrous material to be dyed.

7. The process which comprises dyeing a 1dbrous material with the aid of a dyeing composition containing a dye formed by oxidation, and as another dye, a phenylene dithiourea, one of said dyes being applied first and the other dye being applied later to the fibrous material to be dyed.

8. The process which comprises dyeing a fibrous material with the aid of a dyeing composition containing a member of a group of substances which consists of transformation products of sulfocyanate derivatives of the benzene mamas series, the dyeing being conducted in the presence of an oxidizing agent.

9. The process which comprises dyeing a fibrous material with the aid of a dyeing composition containing a member of a group of substances which consists of transformation products of sulfocyanates of the benzene series, the dyeing being conducted in the presence of an oxidizing agent.

10. The process which comprises dyeing a fibrous material with the aid of a dyeing composition containing a phenylene dithiourea, the dyeing being conducted in the presence of an oxidizing agent.

11. The process which comprises dyeing a fibrous material with the aid of a dyeing composition containing a dye formed by oxidation, and as another dye, a member of a group of substances which consists of transformation products of sulfocyanate derivatives of the benzene series, the dyeing being conducted in the presence of an oxidizing agent.

12. The process which comprises dyeing a fibrous material with the aid of a dyeing composition containing a dye formed by oxidation, and as another dye, a member of a group of substances which consists of transformation products of sulfocyanates of the benzene series, the dyeing being conducted in the presence of an oxidizing agent.

13. The process which comprises dyeing a fibrous material with the aid of a dyeing composition containing a dye formed by oxidation, and as another dye, a phenylene dithiourea, the dyeing being conducted in the presence of an oxidizing agent.

14. The process which comprises dyeing a fibrous material with the aid of a dyeing composition containing a member of a group of substances which consists of transformation prod ucts of sulfocyanate derivatives of the benzene series, the dyeing being conducted in the presence of an oxidizing agent and an acid.

15. The process which comprises dyeing a fibrous material with the aid of a dyeing composition containing a member of a group of substances which consists of transformation products of sulfocyanates of the benzene series, the dyeing being conducted in the presence of an oxidizing agent and an acid.

16. The process which comprises dyeing a fibrous material with the aid of a dyeing composition containing a phenylene dithiourea, the dyeing, being conducted in the presence of an oxidizing agent and an acid.

17. The process which comprises dyeing a fibrous material with the aid of a dyeing composition containing a dye formed by oxidation, and as another dye, a member of a group of substances which consists of transformation products of sulfocyanate derivatives of the benzene series, the dyeing being conducted in the presence of an oxidizing agent and an acid.

18. The process which comprises dyeing a fibrous material with the aid of a dyeing composition containing a dye formed by oxidation, and an another dye, a member of a group of substances which consists of transformation products of sulfocyanates of the benezene series, the dyeing being conducted in the presence of an oxidizing agent and an acid.

19. The process which comprises dyeing a fibrous material with the aid of a dyeing composition containing a member of a group of substances which consists of transformation products of sulfocyanate derivatives of the benzene series, and thereafter removing excess dye, and developing the dye remaining.

20. The process which comprises dyeing a fibrous material with the aid of a dyeing composition containing a phenylene dithiourea, and

thereafter removing excess dye, and developing 1 the dye remaining.

MARTIN BAT'IEGAY.v 

